Azo compounds and material colored therewith



Patented Oct. 14, 1941 AZO COMPOUNDS AND COLORED THEREW'ITH Joseph B. Dickey and James G. McNally, Rochester, N. Y., assignors to Eastman Kodak Com- U pany, Rochester, N. Y., a corporation of New Y, Jersey Serial No. 296,116 l N Drawing. Application September22, 1939,

8 Claims. (cl-260 453) This invention relates to the art of dyeing or coloring. More particularly, it relates to new azo dye compounds and the application of the nuclear non-sulfonated compoundsfor the coloration of organic derivatives of cellulose particu- 5. co pounds avi t e general formula j larly textile material made of or containing an g ven, it relates o e particula ly to azo comorganic derivative of cellulose by dyeing, printpo d of t e above general formula, wherein ing, stenciling or like methods. R andtRi each represents the residue of an aryl I Organic derivatives of cellulose are characternucleus of the benzene series, R2 represents a ized by an indiflerent aflinity for the usual cotyq q ya kyl roup and'R represents e esidue ton and wool dyes especially the ordinary water of said 1,3,5-triazin'e nucleus. .1 soluble dyes. Because of this, it has been neces It W l be understood at y as used herein, sary to develop new dye compounds suitable for Unless otherwise indicated, includes not only unthe dyeing or coloration of materials, such. as substituted alkyl groups such as a methylgroup, textile materials, made of or containing an oran et yl roup, a propy oup, o a butyl p, ganic derivative of cellulose. It is, accordingly, t a so s edfi yl 8 111 $11011 as 1 3. an object of our invention to'provide a new class yet y fi y d yp D BfY-hydroxypropyl, of azo dyes suitable for the dyeing or coloration 'yyd yp epy fiy y fio l l, of organic derivatives of cellulose. Another obor )8sul'foethyl, 'for example. Illustrative of J'ect is to provide a process for the coloration of ha10genmaybementi0ned C lo ne, bromine and organic derivatives of cellulose in which the dye iodine. l Illustrative of eyeloa kyl y e' 0r dyes are applied directlycfrom an aqueous ed y l y a y Y Similarly, suspension to the material undergoing coloralus rative o f y i y be mentioned a fury! tion- A further object is to produce dyeings on radieal slleh as furfuryl or tetrahydrofurfu yl. organic derivatives of cellulose which are of good The azo compounds of our invention can be fastness to light and Washing. Other objects prepared by d zotiz n a primary aminobenzene will hereinafter a ear, c k and coupling the diazonium compound obtained .Typical organic derivatives of cellulose include wi h a 1,3,5- i zine plin mp nd h vin the hydrolyzed as well as the unhydrolyzed .celthe general formula: lulose organic acid esters such as cellulose ace- R2 tate, cellulose formate, cellulose propionate; or l, cellulose butyrate and the hydrolyzed as well as i the unhydrolyzed mixed organic acid esters of R2 and R3. have the meanmg cellulose. such as cellulose acetate-propionate, vlously asslgned to cellulose acetate-butyrate, .and the cellulose In order that our mvemlon may be clearly ethers such as methyl cellulose, ethyl cellulose, n the structllml.frmula of 3 't or benzyl cellulose. While our invention will be azme and numbermg 15 m illustrated more particularly in connection with the coloration of cellulose acetate, a' material to HC4/3\2CH which. the invention is especially adapted, it 40 L 1N will be understood that it applies to the colora- \(V tion of other organic derivatives of cellulose such g as those just mentioned. 7 p

The azo compounds of our invention have the e numbeFmg glveli 18 that Whlch W111 be general formula: ployed herein. Coupllng is belleved to take place through the aryl nucleus of the benzene or naph- 1 thalene series which is attached to the 2-position of the 1,3,5-triazine nucleus. Accordingly,

wherein R represents the residue of an aryl nuno group should be present in this varyl nucleus cleus of the benzene series, R1 represents the in the position in which coupling occurs, and no residue of a member selected from the group congroup which would prevent coupling should be sisting of an aryl nucleus of the benzene series present. 1 and an aryl nucleus of thenaphthalene series, As previously indicated, the nuclear non-sul- R2 represents a member selected from the group fonated azo dye compounds of our invention conconsisting of hydrogen, an alkyl group, an allyl stitute Valuable dyes for the coloration of orgroup, a cycloalkyl group and a furyl group-and R3 represents the residue of a 1,3,5-triazine'nucleus joined through'a nuclear carbon atom to the nitrogen atom shown.

While our invention relates broadly to azo garlic derivatives of cellulose such: as those herefor the coloration of organic derivatives of cellulose but can be employed to color textile materials such as wool and silk. These nuclear sulfonated compounds can be prepared in known fashion. They can be prepared, for example, by the use of previously sulfonated components or by subsequent sulfonation of the unsulfonated compounds. For the dyeing of organic derivatives of cellulose such as cellulose acetate silk,

nuclear non-sulfonated compounds wherein R and R1 represent the residue of an aryl nucleus of the benzene series are generally advantageous.

The following examples illustrate the preparation of the azo dye compounds of our invention.

Example 1 .1 gram mole of o-chloroaniline is dissolved in a mixture of 150 cc. of water and 25 cc. of 36% hydrochloric acid. The resulting solution is then cooled by the addition of ice, or in any Example 3 .1 gram mole of m-anthranilate is diazotized in known fashion and the diazonium compound obtained is coupled with .1 gram mole of 2-5- hydroxyethylphenylamino 4,6 dimethylamino-l, 3,5-triazine. Coupling and recovery of the dye compound formed may be carried out in accordance with the method described in Example 1.

manner desired, to about 0 5 C. and the o-chloroaniline is diazotized by adding, with stirring, 6.9 grams of sodium nitrite dissolved in water while maintaining the temperature at about 0-5" C.

.1 gram mole of 2-(m-methylphenyl) -ethy1- amino-4-amino-6-chloro-1,3,5-trlazine is dissolved in glacial acetic acid and the resulting solution is cooled to a temperature approximating 040 C. The diazonium solution prepared as described above is then slowly added with stirring while maintaining a temperature of 0 10 C. The mixture is allowed to stand for a time after which it is made neutral to Congo red paper by the addition of sodium acetate, Upon completion of the coupling reaction which takes place, the dye compound formed is precipitated by adding water, recovered by filtration, washed with water and dried. The dye compound obtained has the formula:

and colors cellulose acetate silk a yellow shade.

Example 2 HM; alga Q It. It

J V N112 and colors cellulose acetate silk a yellow Shade.

The dye compound obtained has the formula:

and colors cellulose acetate silk a yellow shade.

Example 4 .1 gram mole of p-aminoacetophenone is diazotized in known fashion and the diazonium compound obtained is coupled with .1 gram mole of 2 glyceryl (2 methyl-5'-methoxyphenyl) amino 4,6 tetraethyldiamino 1,3,5 triazine. Coupling and recovery of the dye compound formed may be carried out as described in Example l. The dye compound obtained has the formula:

CHaCHOHCHzOH OCH:

and colors cellulose acetate silk an orange shade.

Example 5 .1 gram mole of p-aminobenzenesulfonamide is diazotized in known fashion and the diazonium compound obtained is coupled with .1 gram mole of 2 sodium p sulfoethyl-(2',5' dimethoxyphenyl) amino 4 ethoxy 6-cyclohexylamino -1,3, 5-triazine. Coupling and recoven of the dye compound formed may be carried out as described in Example 1. The dye compound obtained colors cellulose acetate silk, wool and silk an orange shade.

Example 6 the Z-s-chloroethyl group is converted to a -CzH4 group.

The following tabulation further illustrates the compounds included within the scope of our invention together with the color they produce on cellulose acetate silk. The compounds indicated below may be prepared by diazotizing the amines listed under the heading Amine and coupling;

the diazonium compounds obtained with the compounds specified in the column entitled Coupling component. The diazotizati'on and coupling reactions may, for example, be carried out following the general procedure described in Examples 1 to 6, inclusive.

Color on Amine Coupling component cellulose acetatesilk 1 o-Chloroaniline 2-(m-metl1ylplienyl) amino-4-amino-6-chloro-1,3,5-triai,ine. Yellow. 2 p-Nitroaniline- 2-+hydroxypropylphenylamino-4;6-dihydroxy-l,3,5-triazine. Red. 3 1-amino'2-chl0ro-4 nzene. Z-B-methoxyethylphenylammo-4-sodium-fi-sulfatoethyl- Do.

. I amino-fi-amylamino-l,3,5-triazine. 4 1-ami.no-2-bromo-4-nitrobenzcne 2-(1i1)l51e;nylamino-4-s0dium-fi-sulfatoethoxy-G-lau.rylamino- Do.

nazme. p 5 1-amino-2,4-dinitrobenzene 2-(2',5rdimethoxypheny1)-- -methoxy-fi-hydroxypropyl- Violet.

amino-4-methylamino-fi-butylamino-l,3,5-triazine. 6 lamino-2,4-dinitro-6-bromo-benzene. 2-ggygaerylnaphthyl)amino-4,6-di-B-hydroxyethylamiuo- Blue.

. nazme. 7 Z-amino-5-nitro-phenylmethy1sulfone 2-(fl-hydroxyethyl-5-hydroxy-a-naphthyl)-amino-4,6-di- Do.

amino-1,3,5-triazine. j 8 p-Aminoazo-benzene 2-(m-chlorophenyl-tetrahydrofururyl)-an1ino-4-furfuryl- Orange amino-6-hydroxy-l,3,5triaz1ne. Y a v 9 l-amino-2-chloro-4-nitrobenzene 2-(n-pr0py1-phenyl)amino-4-br0mp-6-l1yd.r0Xy-1,f3,5:triazine Rubine 10 l-amino-2,4-dinitro-6-chlorobenzene Z-(cyclohexyl-phenyl)-amiu0-4,6-d1am1no-l,3,5tr1aziue -,Violet. ll p-Aminoacetophenone 2-(furfuryl-phenyl)-amino-4-sodium-fi-sulfoethylam1no-6- Orange.

amino-1,3,5-triazine; l2 p-Nitroaniline. 2-(allyl-phenyl)-amino-4-am1no-6-furfurylamino-l,3,5-tri- Red.

azme. 13 o-Nitroaniline .z-n-butyl-a-naphthyl)-amin0-4-methoxy-6-amino-1,3,5- Orange.

nazine. l4 l-amino-Z-bromo--nitrobenzene 2-(5-hydroxy-n-naphthy1)-arn.ino-4,6-di-y-hydroxypropyl- Blue.

amino-1,3,5-triazine. 15 l-amino-4-cyano-benzenc 2-g5;-l 1yd.roxyfurfuryl-phenyl)-am1no-4,6-d1ethylamino-l,3, Orange.

-r1azine.

H N C-COH I l6 l-amino-2-hydroxy-4-mtro-benzene- .-HzN-% (I3N\ /CH2 Pmkish-red.

F NH:

r. N (fzHiOH l7 l-amino-2,4-dinitro-6-chloro-benzene- HzN--(I? (ll-N 'Blue.

IlIH /(|iJ-CH:

canon While the nuclear non-sulfonated compounds of our invention possess more or less general application for the coloration of wool and silk, compounds of the character of those numbered 3, 4 and 11 in the above tabulation appear to be more particularly suited for the coloration of wool and silk.

Nuclear sulfonated com-pounds corresponding to the nuclear non-sulfonated compounds shown herein can be prepared by sulfonating said nonsulfonated compounds or by employing sulfonated diazo components. Suitable sulfonated amines which can be diazotized and coupled with any of the coupling components shown herein include, for example, m-sulfanilic acid, p-sulfanilic acid, 1 amino-2-sulfo 4 nitrobenzene, l-amino-Z- nitro-l-sulfo-benzene, 1-amino-2-chloro-l-sulfobenzene and 1-amino-2-sulfol-bromobenzene..

It will be understood that the specific dye compounds given hereinbefore are intended tobeillustrative and not limitative of the invention. Any of the amines disclosed herein may be diazotized and the diazonium compounds obtained coupled with any of the coupling components shown herein to obtain dye compounds included within the scope of our invention.

In order that our invention may be clearly understood, it is here noted that the 1,3,5-triazine invention. Those compounds which are insoluble in water may be advantageously employed for the direct dyeing of textile materials by grinding the dye to a fine powder intimately mixing it.with a suitable dispersing or solubilizing agent and adding the resulting mixture to water or a dilute solution of soap in water to form an aqueous dyebath. Following this known preparation of the dyebath, the textil material or materials to be dyed may be added to the dyebath and the dyeing operation conducted in known fashion. For a more complete description as to how the water insoluble azo dye compoundsof our. invention can be employed for the dyeing of organic derivatives of cellulose, reference may be had to our U. S. Letters Patent No. 2,115,030, issued April 26, 1938. Th water insoluble azo dye compounds of our invention, as previously noted, also possess application for the dyeing of wool and silk and they may be applied to these materials in the same manner as they are applied to organic derivatives of cellulose.

The water soluble dye compounds of our invention may be applied to wool, silk and (depending upon the natur and position of the water solubilizing group) organic derivatives of cellulose textile materials from an aqueous solution of the dye which may contain salt. These water soluble 1. The nuclear non-sulfonated monoazo dye compounds having the general formula:

1?: RN=N-R N-Ra wherein R and R1 each represents the residue member selected from the group consisting of hydrogen, an alkyl group, an allyl group, a cycloalkyl group and a furyl group.

5. Material made of or containing an organic derivative of cellulose and in which said organic derivative of cellulose is colored with a nuclear non-sulfonated azo dye compound having the general formula: I

wherein R represents the residue of an aryl nucleus of the benzene series, R1 represents the of and aryl nucleus of the benzene series containing but one benzene nucleus, R2 represents a member selected from the group consisting of hydrogen, an alkyl group, an allyl group, a cycloalkyl group and a furyl group and R2 represents the residue of a 1,3,5-triazine nucleus joined through a nuclear carbon atom to the nitrogen atom shown.

2. The azo compounds having the general wherein R represents the residue of an aryl nucleus of the benzene series, R1 represents the residue of a member selected from the group consisting of an aryl nucleus of the'benzene series and an aryl nucleus of the naphthalene series, R2 represents a hydroxyalkyl group and R3 represents the residue of a 1,3,5-triazine nucleus joined through a nuclear carbon atom to the nitrogen atom shown.

3. The azo compounds having the general wherein R and R1 'each represents the residue of an aryl nucleus of the benzene series, R2 represents a hydroxyalkyl group and R2 represents the residue of a 1,3,5-triazine nucleus joined through a nuclear carbon atom to the nitrogen atom shown.

4. The azo compounds having the general formula:

wherein R and R1 each represents the residue of an aryl nucleus of the benzene series, R2 represents a hydroxyalkyl group, and X and Y each represents a member selected from the group consisting of a halogen atom, a hydroxyl group, an O-alkyl group and a group, wherein R4 and R5 each represents a residue of a member selected from the group wherein R and R1 each represents the residue of an aryl nucleus of the benzene series, R2 represents a hydroxyalkyl group and R3 represents the residue of a 1,3,5-triazine nucleus joined through a nuclear carbon atom to the nitrogen atom shown.

7. A cellulose acetate colored with a nuclear non-sulfonated azo dye compound having the eneral formula:

wherein R represents the residue of an aryl nucleus of the benzene series, R1 represents the residue of a member selected from the group consisting of an aryl nucleus of the benzene series and an aryl nucleus of the naphthalene series, R2 represents a member selected from the group consisting of hydrogen, an alkyl group, an allyl group, a cycloalkyl group and a furyl group and R3 represents the residue of a 1,3,5-triazine nucleus joined through a nuclear carbon atom to the nitrogen atom shown.

8. A cellulose acetate colored with a nuclear non-sulfonated azo dye compound having the general formula:

wherein R and R1 each represents the residue of an aryl nucleus of the benzene series, R2 represents a hydroxyalkyl group and R2 represents the residue of a 1,3,5-triazine nucleus joined through a nuclear carbon atom to the nitrogen atom shown.

JOSEPH B. DICKEY.

JAMES G. MoNALLY. 

